US3647427A - Germanium and silicon additives to dual-layer electrophotographic plates - Google Patents

Germanium and silicon additives to dual-layer electrophotographic plates Download PDF

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Publication number
US3647427A
US3647427A US65955A US3647427DA US3647427A US 3647427 A US3647427 A US 3647427A US 65955 A US65955 A US 65955A US 3647427D A US3647427D A US 3647427DA US 3647427 A US3647427 A US 3647427A
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Prior art keywords
layer
photosensitive member
germanium
selenium
percent
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US65955A
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Hiroshi Hanada
Nobuo Kitajima
Tatsuo Masaki
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Canon Inc
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Canon Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/043—Photoconductive layers characterised by having two or more layers or characterised by their composite structure
    • G03G5/0433—Photoconductive layers characterised by having two or more layers or characterised by their composite structure all layers being inorganic

Definitions

  • An electrophotographic photosensitive member comprises a layer containing selenium, tellurium and at least one of germanium and silicon as an additive and a layer containing selenium and at least one of germanium and silicon as an additive.
  • This invention relates to a photosensitive member for electrophotography. More particularly it relates to an improvement in a selenium photosensitive member and a panchromatic, durable and highly sensitive photosensitive member for electrophotography.
  • amorphous selenium has been widely used for electrophotographic photosensitive members.
  • Amorphous selenium has advantageously appropriate electric resistance, high sensitivity and low fatigue effect.
  • the photosensitive member mainly composed of amorphous selenium is liable to crystallize at a temperature higher than room temperature and furthermore, the crystallization is disadvantageously accelerated depending upon circumstance conditions such as temperature and light irradiation to which the photosensitive member is subsequently subjected. This crystallization decreases dark resistance of selenium and deteriorates the photosensitive member. The extended degree of crystallization results in short life of the photosensitive member.
  • a selenium layer is laid on an electroconductive base and further a this layer sensitive to red light such as a selenium-tellurium alloy layer is provided thereon.
  • a thin protecting layer composed of selenium-arsenic is laid on the thin layer sensitive to red light.
  • the most effective structure for broadening the photosensitive region is that comprising a layer sensitive to short wavelength, i.e., blue light laminated on a layer sensitive to long wavelength, i.e., red light.
  • a layer sensitive to short wavelength i.e., blue light laminated on a layer sensitive to long wavelength
  • red light i.e., red light
  • the resulting photosensitive member somewhat lacks in photosensitivity for blue light and can not be panchromatic, and further, deterioration of photosensitive property caused by crystallization is not solved.
  • a still another object of this invention is to provide an elec-.
  • trophotographic photosensitive member having various sensitivity, panchromatic property and durability depending upon electrophotographic processes in which the photosensitive member is used.
  • the drawing shows diagrammatically an enlarged cross-sectional view of an embodiment of a photosensitive member according to this invention.
  • the electrophotographic photosensitive member according to this invention has a photoconductive layer composed of a layer l containing selenium, tellurium and at least one of germanium and silicon as an additive laminated with a layer ll.
  • photosensitive member of this invention can also eliminate the necessity of a protecting layer.
  • a selenium-tellurium alloy has a sensitive region at a long wavelength side, i.e., red light, but is easily deteriorated due to crystallization by addition of germanium and/or silicon and becomes unstable. Therefore, the selenium-tellurium alloy can not be used at a base side as an electric charge storing layer.
  • a feature of this invention is that germanium and/or silicon is added to a selenium-tellurium alloy to produce a stable ternary or quaternary alloy and this stable ternary or quaternary alloy is used at a base side as an electric charge storing layer.
  • a layer to be laid on the above mentioned layer is composed of selenium, germanium and/or silicon alloy which has a photosensitive region at blue light, Le, a short wavelength side, and compensates the photosensitive region of the abovementioned selenium, tellurium, germanium and/or silicon alloy layer to give a panchromatic and highly sensitive photosensitive member.
  • the alloy layer is stable and crystallization at the surface hardly occurs so that the alloy layer can be a protecting layer. Thus, any other protecting layer is not necessary and thereby a durable photosensitive member can be produced by using fewer layers than prior art.
  • panchromatic property, durability and sensitivity of a selenium photosensitive member can be improved by using only two layers, and the selenium photosensitive member thus improved is very useful for color electrophotographic processes and can be easily produced at low cost since at most two layers are laminated.
  • an electroconductive base I is made of brass, aluminum, copper and the like in a form of sheet, web, plate, cylinder, drum and other various desired forms with an optional thickness.
  • Metallized paper and glass coated with a metallic film layer such as aluminum, copper iodide and the like may be employed.
  • the surface of the base may be coated with an insulating thin film layer.
  • the base may be omitted.
  • a substantially glassy alloy layer 3 is composed mainly of selenium and an additive, that is, germanium and/or silicon and laminated onto layer 2, and the thickness of layer 3 is usually in a range from about 0.1 to 3p.
  • the layer 3 in cooperation with the lower layer 2 gives the photosensitive member a panchromatic light response, i.e., sufficiently sensitive to a visible light up to a wave length of 4,000A.
  • the contents of germanium and/or silicon is preferable somewhat higher than that in layer 2 and usually ranges from 0.1 to 5 percent to give a sufficiently stable alloy.
  • a most usual structure of photosensitive member according to this invention is that composed of a base and a photoconductive layer consisting of two layers laminated thereon.
  • An insulating layer 4 is not always necessary, but the layer 4 effectively protects the surface of the photosensitive layer and markedly improves the durability.
  • Layer 4 is made of, for example, polyester film.
  • the resulting photosensitive member having the insulating layer 4 may be effectively used for an electrophotographic process as disclosed in Japanese Pat. Publication No. 43/23910, which is employed in Example 1 (infra.).
  • the photosensitive member having an insulating layer as above as far as either the base or the insulating layer is transparent to a radiation to which the photoconductive layer is sensitive, imagewise exposure can be carried out.
  • the'insulating layer is transparent.
  • a switching layer is added to the photosensitive member to record the light image pattern as a resistance pattern for imparting a new function to the photosensitive member.
  • the photosensitive member according to this invention may be produced by various optional methods
  • a representative method is a vapor deposition method. Some examples of vapor deposition method are shown below.
  • Another method is a covapor deposition method comprising placing each component metal of the alloys under vacuum and controlling the temperature of each metal component source to form an alloy coating having a desired percentage of each component metal.
  • the base is maintained at a temperature of about 50 to C. lf desired, a cooling apparatus such as a water cooling plate is used to maintain the base at a constant temperature.
  • a vapor deposition is effected at about 280 C. at about 5X10' mm. Hg for about 1 hour, there is obtained a selenium, tellurium, germanium and/or silicon alloy layer of about 60p. in thickness.
  • the aluminum plate was placed in close contact with a copper plate for controlling temperature kept at about 6070 C. in a vacuum room. Under the aluminum plate at a distance of about 25 cm. therefrom, there is provided a vesselhaving a cover with many small holes. In the vessel is placed an alloy of percent selenium, 15 percent tellurium, and 0.1 percent germanium. A shutter is provided between the base and the metal source.
  • This photosensitive member was panchromatic'to whole visible light and showed a sensitivity as high as about I lux. sec. This sensitivity is more than 10 times the sensitivity of conventional, so-called, Xerographic plates employing seleni- Very clear visible images of high resolving property were produced by developing the latent images with positively charged colored touer. When a liquid developer was used, a higher resolving power was shown.
  • the photosensitive member according to this invention was heated up to various temperatures such as 50, 60, 70 C. and the like to deteriorate it forcibly, and the results were compared with conventional selenium plates. As the results, it was found that the photosensitive member of this invention is as stable as'conventional selenium plates even if a surface insulating layer is not provided on the photosensitive member of this invention. Further, when a surface insulating layer was provided, the photosensitive member according to this invention. Further, when a surface insulating layer was provided, the photosensitive member according to this invention was hardly deteriorated. in addition, the photosensitive member having a surface insulating layer was mechanically stable and the characteristics thereof were hardly changed.
  • EXAMPLE 2 A powder mixture of selenium, tellurium and germanium of above 99.99 percent in purity was sealed in a quartz ampul under vacuum of about mm. Hg. This ampul was heated at about 550 C. for 5 hours to melt the contents. During heating the ampul was rotated to form a homogeneous melt. Then, the ampul was dipped in water to quench a glassy alloy of selenium-tellariumgermanium thus obtained. These procedures were repeated to produce 10 glassy alloys having various contents, indicated as No.l-No.l0. The change of composition ratio was carried out by the change of mixing ratio of selenium, tellurium and germanium powders.
  • the above glassy alloys were respectively applied to an aluminum base by vacuum vaporization to form an alloy layer of 60p thick.
  • the vaporization condition is such that the vacuum is 10 to 10 mm. Hg, the temperature of aluminum base ranges from 60 to 78 C and the temperature of vaporization source is kept at 350 C.
  • Photosensitivity was determined by mounting a photosensitive plate on a rotary electrometer, charging positively, exposing to a 60 w. tungsten lamp and measuring an exposure amount (lux.sec.) required to decrease the potential to onetenth. This exposure amount was expressed as photosensitivity value. The exposure was started at 500 v. for each sample.
  • Dark decay was determined by charging the surface of a photosensitive plate to about +800 v. by using a corona charging device of +6 kv., allowing to stand at a dark place and measuring the time required to decrease the charge to half of the original charge, i.e., to 400 v. The reciprocal of said time is used as a dark decay value for facilitating the comparison with the photosensitivity value and the value of photosensitive plate No.1 is assumed as unit.
  • Photosensitivity values and dark decay values of the photosensitive plates No.1 to No.10 measured as above indicated are shown in the table below.
  • Example 2 Contents of component metal (wt. percent)
  • the above mentio ed glassy alloy was deposited on an aluminum base plate under the same conditions as in Example 2 to form a film of 60p. in thickness by vacuum evaporation deposition. On the resulting alloy layer an alloy layer similar to Example 2 was formed. Thus, 13 kinds of photosensitive plate l-l 3 were produced. By using these photosensitive plates, photosensitivity and durability thereof were measured. The photosensitivity was measured in a manner similar to Example 2. The method for measuring durability is shown below.
  • the photosensitive plate was uniformly positively charged by a corona discharger of +6 kv., and exposed to a light source of a 10 w. tungsten lamp at a distance of 30 cm.
  • Durability is represented by the Sample Photophotosensitive sensitivity plate value Durability nun-n.
  • the photosensitivity value and durability value were 80 percent of the values for germanium additive.
  • EXAMPLE 4 In a manner similar to Example 2, selenium, tellurium and germanium powders; 84.9 percent, 15 percent and 0.1 percent, respectively, were used to prepare a glassy alloy. This glassy alloy was uniformly deposited upon an aluminum base plate by vaporization to form a glassy alloy layer of 40p. thick in a manner similar to Example 1.
  • the photosensitive plate No. 1 without germanium shows poor durability.
  • a secondary alloy layer was prepared without changing the component ratio.
  • the percents of germanium and silicon were 0.05 percent, respectively, and the sum of them was still 0.1 percent; in the glassy alloy No. 8, the percents of germanium and silicon were 5 percent respectively and the sum of them was still 10 percent.
  • a secondary alloy layer was formed to produce photosensitive plate No. l-l4 shown in the following table. The resulting photosensitivity and durability of these photosensitive plates are shown in the following table.
  • An electrophotographic photosensitive member which comprises a first photoconductive layer consisting essentially of selenium, tellurium and from about 0.001 to about 5 weight-percent of an additive selected from the group consisting of germanium and silicon and a second photoconductive layer consisting essentially of selenium and from about 0.1 to about 5 weight-percent of an additive selected from the group consisting of germanium and silicon, said second photoconductive layer having a photoconductive response different from that of said first photoconductive layer.
  • An electrophotographic photosensitive member according to claim 1 in which the first layer is between 20 and p. in thickness.
  • An electrophotographic photosensitive member according to claim 1 in which the content of tellurium in the first layer ranges from 5 to 25 weight-percent.
  • An electrophotographic photosensitive member according to claim 1 in which the second layer is between 0.1 and 3p. in thickness.
  • An electrophotographic photosensitive member according to claim 1 wherein the content by weight-percent of the additive in the second layer is larger than that of the additive in the first layer.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Light Receiving Elements (AREA)
US65955A 1969-08-27 1970-08-21 Germanium and silicon additives to dual-layer electrophotographic plates Expired - Lifetime US3647427A (en)

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JP44067165A JPS4843142B1 (enrdf_load_stackoverflow) 1969-08-27 1969-08-27

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3901703A (en) * 1973-02-03 1975-08-26 Int Standard Electric Corp Xeroradiographic plate
US3941591A (en) * 1969-01-22 1976-03-02 Canon Kabushiki Kaisha Electrophotographic photoconductive member employing a chalcogen alloy and a crystallization inhibiting element
US3966470A (en) * 1973-08-22 1976-06-29 Veb Pentacon Dresden Photo-conductive coating containing Ge, S, and Pb or Sn
US4047945A (en) * 1975-02-18 1977-09-13 Xerox Corporation Xeroprinting master and process
US4088485A (en) * 1973-12-07 1978-05-09 Xerox Corporation Graded bandgap xerographic plate
JPS54145537A (en) * 1978-05-04 1979-11-13 Canon Inc Preparation of electrophotographic image forming material
US4281051A (en) * 1978-11-29 1981-07-28 Ricoh Company, Ltd. Three color electrostatographic process
JPS56161551A (en) * 1980-05-16 1981-12-11 Canon Inc Image forming member for electrophotography
US4335194A (en) * 1978-02-20 1982-06-15 Ricoh Company, Ltd. Two color electrophotographic process and material
US4451546A (en) * 1982-03-31 1984-05-29 Minolta Camera Kabushiki Kaisha Photosensitive member
US4481270A (en) * 1983-04-28 1984-11-06 Ricoh Systems, Inc. Photoreceptor containing squaric acid methine dyes
US4491626A (en) * 1982-03-31 1985-01-01 Minolta Camera Kabushiki Kaisha Photosensitive member
US4532198A (en) * 1983-05-09 1985-07-30 Canon Kabushiki Kaisha Photoconductive member
US4990420A (en) * 1988-08-05 1991-02-05 Fuji Electric Co., Ltd. Electrophotographic photoreceptor with doped Se or Se alloy interlayer

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2803541A (en) * 1953-05-29 1957-08-20 Haloid Co Xerographic plate
US3307089A (en) * 1963-03-16 1967-02-28 Matsushita Electric Ind Co Ltd Semiconductor device showing the effect of storing charges of single polarity
US3355289A (en) * 1962-05-02 1967-11-28 Xerox Corp Cyclical xerographic process utilizing a selenium-tellurium xerographic plate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2803541A (en) * 1953-05-29 1957-08-20 Haloid Co Xerographic plate
US3355289A (en) * 1962-05-02 1967-11-28 Xerox Corp Cyclical xerographic process utilizing a selenium-tellurium xerographic plate
US3307089A (en) * 1963-03-16 1967-02-28 Matsushita Electric Ind Co Ltd Semiconductor device showing the effect of storing charges of single polarity

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3941591A (en) * 1969-01-22 1976-03-02 Canon Kabushiki Kaisha Electrophotographic photoconductive member employing a chalcogen alloy and a crystallization inhibiting element
US3901703A (en) * 1973-02-03 1975-08-26 Int Standard Electric Corp Xeroradiographic plate
US3966470A (en) * 1973-08-22 1976-06-29 Veb Pentacon Dresden Photo-conductive coating containing Ge, S, and Pb or Sn
US4088485A (en) * 1973-12-07 1978-05-09 Xerox Corporation Graded bandgap xerographic plate
US4047945A (en) * 1975-02-18 1977-09-13 Xerox Corporation Xeroprinting master and process
US4335194A (en) * 1978-02-20 1982-06-15 Ricoh Company, Ltd. Two color electrophotographic process and material
JPS54145537A (en) * 1978-05-04 1979-11-13 Canon Inc Preparation of electrophotographic image forming material
US4281051A (en) * 1978-11-29 1981-07-28 Ricoh Company, Ltd. Three color electrostatographic process
JPS56161551A (en) * 1980-05-16 1981-12-11 Canon Inc Image forming member for electrophotography
US4451546A (en) * 1982-03-31 1984-05-29 Minolta Camera Kabushiki Kaisha Photosensitive member
US4491626A (en) * 1982-03-31 1985-01-01 Minolta Camera Kabushiki Kaisha Photosensitive member
US4481270A (en) * 1983-04-28 1984-11-06 Ricoh Systems, Inc. Photoreceptor containing squaric acid methine dyes
US4532198A (en) * 1983-05-09 1985-07-30 Canon Kabushiki Kaisha Photoconductive member
US4990420A (en) * 1988-08-05 1991-02-05 Fuji Electric Co., Ltd. Electrophotographic photoreceptor with doped Se or Se alloy interlayer

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GB1322358A (en) 1973-07-04
JPS4843142B1 (enrdf_load_stackoverflow) 1973-12-17
DE2042592B2 (enrdf_load_stackoverflow) 1974-03-28
DE2042592A1 (de) 1971-03-18

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